Method of controlling acarids with certain oxime esters

ABSTRACT

Acaricidal, fungicidal and bacterial compounds having the formula IN WHICH HAL IS CHLORINE, BROMINE OR IODINE, R1 is (1) hydrogen, (2) lower alkyl, (3) aryl, (4) nuclear substituted derivatives thereof in which the substituents are halogen, nitro, lower alkoxy, lower alkyl, or cyano and (5) haloalkyl, and R2 is (1) aryl, (2) nuclear substituted derivatives thereof in which the substituents are halogen, cyano, nitro, lower alkoxy, or lower alkyl, (3) styryl, (4) nuclear substituted styryl, in which the substituents are halogen, cyano, nitro, lower alkoxy or lower alkyl, (5) benzyl, (6) nuclear substituted benzyl in which said substituents are halogen, cyano, nitro, lower alkoxy or lower alkyl, (7) phenethyl, (8) nuclear substituted phenethyl in which the substituents are halogen, cyano, nitro, lower alkoxy, or lower alkyl, (9) cycloalkyl having three to six carbon atoms, and (10) furyl.

United States Patent [191 Gutman et .al.

[45] Jan. 2, 1973 [54] METHO OF CONTROLLING ACARIDS WITH CERTAIN OXIMEESTERS [75] ravefirii a Arnold D'I' @IItTikihfSIaTRhTid,

[62] Division of Ser. No. 746,309, July 22, 1968, Pat. No.

[52] US. Cl. ..424/327, 424/285, 424/304 [51] Int. Cl. ..A0ln 9/24 [58]Field of Search ..424/304, 327, 285; 7l/l2l;

[ 56] References Cited UNITED STATES PATENTS 3,063,823 11/1962 Kuhleeta'l. ..7l/l2l OTHER PUBLICATIONS Chemical Abstracts 55 z 23555(e)I961.

Primary Examiner-Albert T. Meyers Assistant Examiner-Norman A. DrezinAttorney-Wayne C. Jaeschke [5 7] ABSTRACT Acaricidal, fungicidal andbacterial compounds having the formula in which hal is chlorine, bromineor iodine, R is (1) hydrogen, (2) lower alkyl, (3) aryl, (4) nuclearsubstituted derivatives thereof in which the substituents are halogen,nitro, lower alkoxy, lower alkyl, or cyano and (5) haloalkyl, and R is(l) aryl, (2) nuclear substituted derivatives thereof in which thesubstituents are halogen, cyano, nitro, lower alkoxy, or lower alkyl,(3) styryl, (4) nuclear substituted styryl, in which the substitucntsare halogen, cyano, nitro, lower alkoxyor lower alkyl, (5) benzyl, (6)nuclear substituted benzyl in which said substituents are halogen,cyano, nitro, lower alkoxy or lower alkyl, (7) phencthyl, (8) nuclearsubstituted phenethyl in which the sub stituents are halogen, cyano,nitro, lower alkoxy, or lower alkyl, (9) cycloalkyl'having three to sixcarbon atoms, and (10) furyl.

13 Claims, No Drawings METHOD OF CONTROLLING ACARIDS WITH CERTAIN OXIMEESTERS This application is a division of copending application Ser. No.746,309, filed July 22, 1968 now US. Pat. No. 3,592,920.

This invention relates to novel chemical compounds and to their use asherbicides and acaricides and in conche mical compounds are certain ketooxime esters.

The compounds of the present invention are those having the formula inwhich hal is a member selected from the group consisting of chlorine,bromine and iodine, preferably chlorine, R is a member selected from thegroup consisting of l hydrogen, (2) lower alkyl, preferably having fromone to six carbon atoms, (3) aryl, preferably phenyl, (4) nuclearsubstituted derivatives thereof in which the substituents are selectedfrom the group consisting of halogen, nitro, lower alkoxy, preferablyhaving from'one to four carbon atoms, more preferably methoxy, loweralkyl, preferably having one to four carbon atoms, more preferably,methyl, and cyano and (5) haloalkyl, preferably having from one to fourcarbon atoms; most preferably chloromethyl, and R is a member selectedfrom the group consisting of l) aryl, preferably phenyl (2) nuclearsubstituted derivatives thereof in which the substituents are selectedfrom the group consisting of halogen, preferably chlorine and bromine,cyano, nitro, lower alkoxy, preferably having from one to four carbons,more preferably methyl, (3) styryl, (4) nuclear substituted styryl, inwhich the substituents are selected from the group consisting ofhalogen, preferably chlorine and bromine, cyano, nitro, lower alkoxy,preferably having. one to four carbon atoms, .more preferably methoxy,and lower alkyl, preferably having one to four carbon atoms, morepreferably methyl, (5) benzyl, (6) nuclear substituted benzyl in whichsaid substituents are selected from the group consisting of halogen,preferably-chlorine and bromine, cyano, nitro, lower alkoxy, preferablyhaving one to four carbon atoms, more preferably methoxy and loweralkyl, preferably having one to four carbon atoms, more preferablymethyl, (7) phenethyl, (8) nuclear substituted phenethyl in which thesubstituents are selected from the group consisting of halogen,

' preferably chlorine and bromine, cyano, nitro, lower Representativecompounds of this invention are: 1 ,3-dichloro-2-propanone-0-( benzoyl)oxime trolling fungi and bacteria. More particularly, the

l,3-dichloro-2-propanone-0-(napththoyl) oxime l,3-dichloro-2-propanone-0-(p-chlorobenzoyl) oxime l,3-dichloro-2-propanone-O-( 3,4-

dichlorobenzoyl)oxime l ,3-dichloro-2-propanone-0-( 3,4,5-trimethoxybenzoyl) oxime l ,3-dichloro-2-propanone-0-(p-bromobenzoyl) oxime l,3-dichloro-2-propanone-0-(p-idobenzoyl) oximel,3-dichloro-2-propanone 0-( p-fluorobenzoyl) oximel,3-dichloro-2-propanone-0-(4-butylbenzoyl) oxime 1,3-dichloro-2-propanone-0-(4-cyanobenzoyl) oxime l,3-dichloro-2-propanone-O-( 4-nitrobenz'oyl) oxime l,3-dichloro-2-propanone-0-( 4-in-butoxybenzoyl) oxime 1,3-dichloro-2propanone-0-(cinnamoyl) oxime l,3-dichloro-2-propanone-0-(p-chlorocinnamoyl) oximel,3-dichloro-2-propanone-0-( 3 ,4-dichlorocinnamoyl) oxime I1,3-dichloro-2-propanone-0-(3,4,5-trimethoxycinnamoyl) oxime1,3-dichloro-2-propanone-0-( p-bromocinnamoyl) oxime1,3-dichloro-2-propanone-0-(p-iodocinnamoyl) oximel,3-dichloro-2-propanone-O-( p-fluorocinnamoyl) oximel,3-dichloro-2-propanone-0-(4-t-butyl cinnamoyl) oxime 1,3-dichloro-2-propanone-0-(4-n-butyoxycinnamoyl) oximel,3-dichloro-2-propanone-0-(4cyanocinnamoyl) oximel,3-dichloro-2-propanone-0-(4-nitrocinnamoyl) oxime l,3-dichloro-2-propanone-0-(hydrocinnamoyl) oximel-chloro-2-propanone-0-(benzoyl) oxime l-chloro-2-octanone-O-(benzoyl)oxime l,6-dichloro-2-hexanone-0-(benzoyl) oximel,3,-dibromo-2-propanone-0-(benzoyl) oxime1,3-diiodo-2-propanone-0-(benzoyl) oximel-chloro-3-bromo-2-propanone0-(benzoyl) oximel-fluoro-2-propanone-0-(benzoyl) oxime chloroethanal-O-(benzoyl) oximea-chloroacetophenone-0-( benzoyl) oximea-bromo-4-chloro-acetophenone-0-(benzoyl) oximea-chloro-4-nitroacetophenone-0-( benzoyl) oximea-chloro-4-cyanoacetophenone-0-(benzoyl) oximeor-chloro-4-methoxyacetophenone0-(benzoyl) oximea-chloro-4-methylacetophenone-0-( benzoyl) oxime The compounds of thepresent invention are particularly useful as acaricides. The compoundsare also useful in inhibiting the growth of bacteria and fungi. Also,the compounds of the present invention find use as herbicides,especially in post-emergent control of weeds.

The compounds of the present invention can be prepared by reacting acompound of the formula hill-011g C=NU1I in which hal and R are asdefined before with a compound of the formula halo in which halo ischlorine or bromine and R is a radical as defined as above.

The above reaction yields compounds of the formula EXAMPLE 1.

l,3-dichloroacetone--( 3-methylbenzoyl) oxime.

63.5 gms. (0.50 moles) 1,3-dichloropropanone, 69.5 gms. (1.00 moles)hydroxylamine hydrochloride, 250 ml. ethanol and 25 ml. of water arecombined and heated under reflux for four hours. The cooled mixture ispoured into 500 ml. of water. The aqueous solution is extracted with 3100 ml. portions of chloroform. The chloroform phases are combined anddried-with anhydrous MgSO The chloroform is evaporated to give 66.3g.(93.6 I percent of theory) of 1,3- dichloroacetoneoxime,

-C1H2C C=NOH ClHzC 14.2 gms (0.1 moles of 1,3-dichloroacetoneoximeprepared according to the above procedure and 14.4

' gms. (0.093 moles) of m-toluoyl chloride are combined in 200 ml. ofbenzene and the mixture is cooled to C. 12.1 gms. (0.12 moles) oftriethylamine are added dropwise while keeping the temperature between15 C. with stirring. The reaction is continued 30 minutes after thecompletion of the addition of triethylamine. The mixture is washed twicewith water, twice with NaHCO and again twice with water. The benzenephase is dried with anhydrous MgSO, and evaporated to give 1 1.1 g. of1,3-dichloroacctone-O-(3- methylbenzoyl) oxime,

The following is a table of certain selected compounds that are preparedaccording to the procedure described hereto. Compound numbers areassigned to each compound and are used throughout the remainder of theapplication- TABLE I |11l-Cll2 0 ll C NOC-R Compound Number hal R '1' lchloro chloromethyl phenyl 2 chloro chloromethyl 2-chlorophenyl 3 chlorochloromethyl 4-chlorophenyl 4 chloro chloromethyl 3,4-dichlorophenyl 5chloro chloromethyl 3-chlorophenyl 6 chloro chloromethyl 4-bromophenyl 7chloro chloromethyl 2-bromophenyl 8 chloro chloromethyl 4-methoxyphenyl9 chloro chloromethyl 2-methoxyphenyl 10 chloro chloromethyl3,4,5-trimethoxyphenyl 1 1 chloro chloromethyl 4-nitrophenyl l2 chlorochloromethyl 3-nitrophenyl l3 chloro chloromethyl 3,5-dinitro-phenyl l4chloro chloromethyl 4-methylphenyl 15 chloro chloromethyl 3-methylphenyll6 chloro chloromethyl 2-methylphenyl l7 chloro chloromethyl styryl 18chloromethyl 2-furyl l9 chloromethyl benzyl 20 chloromethyl Cll 3Ol13-21 chloro chloromethyl cyclohexyl 22 chloro phenyl 4-chlorophenyl 23chloro hydrogen phenyl 24 chloro hydrogen phenyl 25 chloro hydrogen4-chloropheny1 26 chloro hydrogen 4-nitrophenyl 27 chloro hydrogenstyryl 28 chloro hydrogen 4-methoxyphenyl 29 chloro hydrogen4-methylphenyl The following tests illustrate utility of the compoundsin controlling fungi and bacteria and as acaricides.

In vitro vial test. This test measures the bactericidal and fungicidalproperties of a compound when in contact with a growing bacterium orfungus. The test is conducted by partially filling two l-ounce vialswith malt broth and one l-ounce vial with nutrient broth. Next, the testcompound is added to the vials at a certain concentration, expressed inparts per million, and mixed with the broth. A water suspension ofspores of the desired fungi or cells of the desired bacteria (oneorganism per vial) is added. The vials are then sealed and incubated forone week; at this time the vials are examined and the results recorded.Table IV shows the results of various compounds tested by the in vitrovial test.

TABLE II Concentration (p.p.m.) which inhibited growth.*

Fungus Bacteria Aspergillus Penicillium Stapylococcus Compound Niger sp.Aureus 1 0.25 (0.13) (25) 2 (5) (l) 25 3 (0.13) (0.13) 25 4 (0.13)(0.25) 10 5 (0.25) (0.25) 10 6 (0.25) (0.25) (10) 7 (0.5) 1 50 3 9 5 2550 10 (25) 50 11 (5) (0.5) 25 12 (5) (1) l5 13 50 (50) 50 14 (0.5)(0.25) 5 15 0.5 (0.5) 5 16 10 (5) 10 17 (0.5) (0.25) 25 18 (0.5) (0.25)25 l (0.5) (0.5) (25) 20 (10) (1) (10) 21 (0.25) (25) 22 (50) (50) 50 23(10) 50 24 5 10 50 25 5 5 50 '26 (25) (10) 50 27 50 (10) 50 28 50 (25)50 29 50 25 50 partial control As can be seen by the test results, thecompounds of the present invention find particular utility asbactericides and fungicides. The compounds can be applied in a varietyof ways at various concentrations. They can be combined with suitablecarriers and applied as dusts, sprays or drenches. The amount appliedwill depend on .the nature of the utility. The rate of application canalso vary with the microbiological use intended.

Acaricidal Evaluation Test. The two-spotted mite, Tetranychus telarius(Linn.), was employed in tests for acaricides. Young pinto bean plantsin the primary leaf stage were used as the host plants. The young pintobean plants were infested with several hundred mites. Dispersions ofcandidate materials were prepared by dissolving 0.1 gram in, 10 ml. of asuitable solvent,

usually acetone. Aliquots of the toxicant solutions were suspended inwater containing 0.0l75% v/v S ponto 221", an emulsifying agent, theamount of water being sufficient to give concentrations of activeingredient ranging from 0.25 percent to 0.001 percent. The testsuspensions were then sprayed on the infested pinto bean plants. Afterseven days, mortalities of post-embryonic and ovicidal forms weredetermined. The percentage of kill was determined by comparison withcontrol plants which had not been sprayed with the candidate compounds.The LD-50 value was calculated using well-known procedures. These valuesare reported under the columns PE and Eggs in Table l1.

TABLE III Compound Number Acaricidal Activity PE Eggs Various techniquesor methods can be employed for contacting acarids with the compounds.For example,

spray formulations can be prepared by dissolving a compound in suitableorganic solvent such as soluene, xylene, benzene, and the like, andsubsequent dispersion of this solution in water in the presence of asurface active wetting or emulsifying agent. Another method by which theacaricidal agents of the present invention can be applied is in the formof dispersible powders, preferably as homogeneous free-flowing dustscommonly formulated by mixing the active component with finely dividedsolids or carriers such as talc, natural clays, diatomaceous earth,various flours such as walnut shell, wheat and the like. The details ofcompounding and application are well known to those skilled in the art.

As previously stated, the compounds of this inven tion are useful asherbicides and especially as postemergence type herbicides. Thepost-emergence herbicide testing procedure is as follows:

Post-emergence Herbicide Test. The seeds of crabgrass, watergrass, redoats,-Indian mustard, curly dock and pinto bean were planted inindividual rows in Santav Cruz sandy loam soil. After growing for twoweeks under greenhouse conditions, the plates were four to six inchestall. Thereafter, the candidate test compound was applied to the foliageby means of an overhead spray while the flat moved under the spray on amoving table. A concentration of 0.5 percent of active compound in thespray was used at a rate equivalent to approximately 60 lbs./acre. Twoweeks after treatment, the injury results were recorded and it wasdetermined that the compounds of the invention have utility asherbicides, especially post-emergence herbicides.

Compound Numbers 1, 4 and 17 were selected for further evaluation andwere found to give generally excellent control at the application rateof 2 pounds per acre of certain weed species as is shown in Table IV.

TABLE IV Percent Control Compound Crab- Number grass Pigweed Mustard Thecompounds of the present invention as postemergence herbicides and canbe applied in a variety of ways at various concentrations. They may becombined with suitable carriers and applied as dusts, sprays ordrenches. The amount applied will depend upon the nature of the weeds orplants to be controlled and the rate of application may vary from 1 to80 pounds per acre. One particularly advantageous way of applying thecompounds is as a narrow band along a row crop, straddling the row. Itis not necessary that the phytotoxic compositions be admixed with thesoil particles and these compositions can be applied merely by sprayingthe sprinkling the surface of the soil. The phytotoxic compositions ofthis invention can also be applied to irrigation' water supplied to thefield to be treated. This method of application permits the penetrationof the compositions into the soil as the water is absorbed therein. Dustcompositions, granular compositions or liquid formulations applied tothe surface of the soil can be distributed below the surface of the soilby conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain otheradditaments, for example fertilizers, pesticides and the like, used asadjuvant or in combination with any of the above-described adjuvants.Other phytotoxic compounds useful in combination with theabove-described compounds include for example 2,4- dichlorophenoxyaceticacids, 2,4,5-trichlorophenoxyacetic acid, 2 methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof;triazine derivatives, such as 2,4-bis (3-methoxypropylamino)-6-methylthio-S-triazine; 2-chloro-4-ethylamino-6-isopropylamino-S-triazine, and 2-ethylamino-4-isopropylamino-6-methylmercapto-S-triazine, urea derivatives, such as3-(3,4-dichlorophenyl)-1,1- dimethyl urea and3-(p-chlorophenyl)-l,l-dimethyl urea and acetamides such as N,N diallyl-achloroacetamide, N-(a-chloroacetyl) hexamethylene imine, andN,N-diethyl-a-bromacetamide, and the like; benzoic acids such as 3-amino-2,S-dichlorobenzoic and; thiocarbamates, such as S-propyldipropylthiocarbamate; S-ethyl-dipropylthiocarbamate,S-ethylcyclohexyl-ethyl-thio-carbamate, S-ethylhexahydrolH-azepine-l-carbothioate and the like. Fertilizers useful incombination with the active ingredients include for example ammoniumnitrate, urea and superphosphate. Other useful additaments includematerials in which plant organisms take root and grow such as compost,manure, humus, sand and the like.

The concentration of a compound of the present invention, constitutingan effective amount in the best mode of administration in the utilitydisclosed is readily determinable by those skilled in the art.

We claim: l, A method of controlling acarids comprising applying theretoan acaricidally effective amount of the compound having the formula inwhich hal is a member selected from the group consisting of chlorine,bromine and iodine, R is a member selected from the group consistingof 1) hydrogen, (2) lower alkyl having 1 to 6 carbon atoms, (3) phenyl,(4) nuclear substituted derivatives thereof in which the substituentsare selected from the group consisting of halogen, nitro, lower alkoxyhaving one to four carbon atoms, lower alkyl having 1 to 4 carbon atoms,and cyano and (5) haloalkyl having 1 to 4 carbon atoms, and R is amember selected from the group consisting of l phenyl, (2) nuclearsubstituted derivatives thereof in which the substitutents are selectedfrom the group consisting of halogen, cyano, nitro, lower alkoxy havingone to four carbon atoms, and lower alkyl having one to four carbonatoms, (3) styryl, (4) nuclear substituted styryl, in which thesubstituents are selected from the group consisting of halogen, cyano,nitro, lower alkoxy having one to four carbon atoms, and lower alkylhaving 1 to 4 carbon atoms, (5) benzyl, (6) nuclear substituted benzylin which said substituents are selected from the group consisting ofhalogen, cyano, nitro, lower alkoxy having one to four carbon atoms, andlower alkyl having one to four carbon atoms, (7) phenethyl, (8) nuclearsubstituted phenethyl in which the substituents are selected from thegroup consisting of halogen, cyano, nitro, lower alkoxy having one tofour carbon atoms, and lower alkyl having one to four carbon atoms, (9)cycloalkyl having 3 to 6 carbon atoms, and (10) furyl.

2. The method of claim 1 in which R is chloromethyl and R is phenyl.

3. The method of claim 1 in which R is chloromethyl and R is a halogensubstituted phenyl.

4. The method of claim 3 in which R is 3- chloromethyl and R is loweralkyl substituted phenyl.

12. The method of claim 39 in which R is 4- methylphenyl.

13. The method of claim 1 chloromethyl and R is styryl.

in which R is

2. The method of claim 1 in which R1 is chloromethyl and R2 is phenyl.3. The method of claim 1 in which R1 is chloromethyl and R2 is a halogensubstituted phenyl.
 4. The method of claim 3 in which R2 is3-chlorophenyl.
 5. The method of claim 3 in which R2 is 4-chlorophenyl.6. The method of claim 3 in which R2 is 3,4-dichlorophenyl.
 7. Themethod of claim 3 in which R2 is 2-bromophenyl.
 8. The method of claim 3in which R2 is 4-bromophenyl.
 9. The method of claim 1 in which R1 ischloromethyl and R2 is nitrophenyl.
 10. The method of claim 37 in whichR2 is 3-nitrophenyl.
 11. The method of claim 1 in which R1 ischloromethyl and R2 is lower alkyl substituted phenyl.
 12. The method ofclaim 39 in which R2 is 4-methylphenyl.
 13. The method of claim 1 inwhich R1 is chloromethyl and R2 is styryl.